Development of Sensitizers and Chemiluminescent Reagents intending to create new Super-function

我们探索了生成新超函数的函数累加系统。近年来，许多超功能化学传感器的研究都采用了络合增强荧光技术。然而，基于金属离子的功能化学发光体系尚未见报道。我们提出了第一个潜在的信号系统，结合了螯合能力和CL特性。我们合成了4，5-二苯基-2-(2-吡啶)-咪唑，并发展成具有螯合功能的2-(2-羟基苯基)-4，5-二苯基咪唑1。在KOH/MeOH引发下，1的化学发光效率是过氧化洛芬的0.28倍。当触发基改为TBAF/THF时，在干DMF中的效率是530倍。在单线态氧检测器存在下，从洛芬过氧化氢的反应中检测到单线态氧。为了考察取代基对单线态氧形成的影响，测试了2-(对取代苯基)碘酚过氧化氢。电子吸引基团有助于单线态氧的有效形成，而电子供体基团则增强了化学发光。作为第二个例子，我们合成了一个具有乙二胺主体功能的2，11-二氮杂[3，3]对环(9，10)并[9，10]并[9，10]杂环化合物。此外，我们还报道了一个独特的，意想不到的重排反应，从[苯并茂]双平面分子转变为储能化合物和氮杂环化合物。我们在双平面分子的功能化学和光化学方面取得了突出的研究目标。我们非常感谢KAKEN基金的资金支持。

We have explored function-accumulating system for generation of a new super-function. Recently many investigations on chemo-sensors as the super-function have employed chelation-enhanced fluorescence. However, metal ion-based functional chemi luminescent systems have not been reported for the lophines. We presented the first potential signaling system incorporating a chelating ability and CL property. We have prepared 4,5-diphenyl-2-(2-pyridyl)-imidazole and developed to 2-(2-hydroxyphenyl)-4,5-diphenylimidazole 1 bearing a chelating function. The CL efficiency of 1 was 0.28 times that of lophine peroxide on initiation with KOH/MeOH. When the trigger base was changed to TBAF/THF, the efficiency was 530-fold in dry DMF. Singlet oxygen was detected from the reaction of lophine hydroperoxides in the presence of a singlet oxygen detector. In order to examine the substituent effect on the formation of singlet oxygen, 2-(p-substituted phenyl) lophine peroxides were tested. An electron-attracting group contributed to the efficient formation of singlet oxygen, while an electron-donating group enhanced the chemiluminescence. As the second example, a 2,11-diaza[3,3]paracyclo(9,10)anthracenophane derivative possessing an ethylenediamine host function has been prepared.Further we reported a unique-unexpected rearrangement from [benzene anthracene]biplanemers to energy-stored compounds and a azepine chemistry as a side work.We have achieved outstanding research goals in their functional chemistry and photochemistry of biplanemers as shown above. We are very much grateful for the financial support from the KAKEN fund.